WO2018006635A1 - Procédé de fabrication d'un film polymère poreux - Google Patents

Procédé de fabrication d'un film polymère poreux Download PDF

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WO2018006635A1
WO2018006635A1 PCT/CN2017/081790 CN2017081790W WO2018006635A1 WO 2018006635 A1 WO2018006635 A1 WO 2018006635A1 CN 2017081790 W CN2017081790 W CN 2017081790W WO 2018006635 A1 WO2018006635 A1 WO 2018006635A1
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chloride
bis
compound
polymer
triptycene
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PCT/CN2017/081790
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English (en)
Chinese (zh)
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周浩力
陶飞
金万勤
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南京工业大学
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Priority to JP2017566708A priority Critical patent/JP6549737B2/ja
Priority to EP17803762.8A priority patent/EP3323500B1/fr
Priority to US15/579,205 priority patent/US10799836B2/en
Publication of WO2018006635A1 publication Critical patent/WO2018006635A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0095—Drying
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/46—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/28—Degradation or stability over time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/755—Membranes, diaphragms

Definitions

  • the invention relates to a preparation method of a polymer separation membrane, and belongs to the field of polymer polymer membranes.
  • VOCs volatile organic compounds
  • various mature VOCs treatment processes such as absorption method, adsorption method, condensation method, biological method and membrane separation method have been developed in the industry.
  • the membrane separation method Compared with several other separation methods, the membrane separation method has the advantages of low energy consumption, simple operation, no secondary pollution, high safety performance, etc., and is called the gas separation technology with the most development application prospect.
  • the reticulated polymer material can be prepared by using the reaction sites and derivatization sites rich in triptycene, and the network-like microporous polymer has the characteristics of amorphous structure, high stability and organic micropores. Therefore, it has a wide range of applications in the fields of gas adsorption, hydrogen storage, gas separation and the like.
  • the microporous polymer of the network structure is difficult to dissolve in common solvents and is prone to aging, thus greatly limiting the popularization and application of materials.
  • the object of the present invention is to provide a method for preparing a tripentyl polymer separation membrane.
  • the method solves the problem that the network structure polymer material is insoluble, and breaks the network structure polymer because it is difficult to dissolve and is difficult to be aged. Limitations of application in separation membranes.
  • the object of the invention can be achieved by the following measures:
  • a method for preparing a triptyl polymer separation membrane comprising the steps of:
  • triptycene containing a reactive group is used as a first monomer
  • a diacid chloride compound is used as a second monomer
  • a diamino compound containing an ether bond is used as a third monomer, in the presence of an acid binding agent.
  • the polymerization was carried out underneath. After the reaction, the polymer was separated and further washed with methanol, followed by dissolution in an aprotic solvent to prepare a separation membrane.
  • the polyamide polymer of the network structure prepared by the method can be dissolved not only in the aprotic solvent, but also the separation membrane thus obtained has higher uniformity and better separation performance.
  • the step of cleaning the polymer is specifically: the polymer solution is poured into deionized water for precipitation, and then the precipitate is filtered, and the precipitate is washed with methanol several times, followed by filtration, and the filtrate is filtered. After drying, the triptycene polymer is obtained; under a preferred condition, the filtrate is dried by oven drying, and the drying temperature is 40 ° C to 120 ° C.
  • the reactive group-containing triptycene compound of the present invention is selected from a hexaamino-substituted tri-disc compound or a derivative thereof, a tetraamino-substituted tri-disc compound or a derivative thereof, a triamino-substituted tri-disc compound or Any one of a derivative, a diamino-substituted tri-disc compound or a derivative thereof.
  • the triptycene compound containing a reactive group is selected from the group consisting of 2,3,6,7,12,13-hexaaminotrimonene, 2,3,6,7-tetraaminotrimonene, 2,6,14-triaminotriptyrene, 2,7,14-triaminotripadene, 9,10-dimethyl-2,6,14-triaminotripreene, 9,10-dimethyl Any one of benzyl-2,7,14-triaminotriptyrene, 2,6-diaminotriptyrene, 2,7-diaminotriptylene, and the like.
  • the triptycene compound containing a reactive group is selected from the group consisting of 2,6,14-triaminotriptyrene, 2,7,14-triaminotripadene, 9,10-dimethyl Base-2,6,14-triaminotriptyr, 9,10-dimethyl-2,7,14-triaminotriptyrene, 2,6-diaminotriptyrene, 2,7-diamino One of triptycene.
  • the diacid chloride compound in the present invention may be selected from the group consisting of oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, adipyl chloride, 1,7-peptanedioyl chloride, sebacic acid chloride, hexafluoroglutaryl chloride, and sebacic acid chloride.
  • 1,8-dioctanoyl chloride 1,8-dioctanoyl chloride, terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, 1,4-cyclohexanedioyl chloride, trimesic acid chloride, fumarate, tetrafluoro Phthalic acid chloride, hexafluoroglutaryl chloride, dodecanedioyl dichloride, 1,8-dioctanoyl chloride, 2,6-chloroformylpyridine, 1,4-phenylene diacryloyl chloride, trans- 3,6-bridge-methylene-1,2,3,6-tetrahydrophthaloyl chloride, 5-amino-2,4,6-triiodo-1,3-benzenedicarboxylic acid chloride, couple Nitrobenzene-4,4'-dicarbonyl chloride, 4,4'-biphenyldiacetyl
  • the diacid chloride compound of the present invention may be selected from the group consisting of oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, adipyl chloride, 1,7-peptanedioyl chloride, sebacic acid chloride, and para-benzene.
  • oxalyl chloride malonyl chloride
  • succinyl chloride glutaryl chloride
  • adipyl chloride 1,7-peptanedioyl chloride
  • sebacic acid chloride and para-benzene.
  • Diformyl chloride isophthaloyl chloride,
  • the diamino compound containing an ether bond in the present invention may be a diamino compound having an ether bond with or without a fluorine group, such as bis(3-aminopropyl)ether or 3,4-diaminodiamine.
  • the diamino compound containing an ether bond in the present invention is selected from the group consisting of 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis[(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(trifluoromethyl)-4,4-diaminophenyl ether, 1,3-bis(2-trifluoromethyl-4-amino In phenoxy)benzene, 1,4-bis(2-trifluoromethyl-4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane One.
  • the molar ratio of the triptycene compound containing the reactive group, the diacid chloride compound and the diamino compound containing the ether bond is 1:1.0 to 20.0:0.2 to 10; preferably: 1:2.0 to 10.0: 0.5 to 5; the molar amount of the acid binding agent is 1 to 10 times, preferably 1.5 to 5 times the molar amount of the diacid chloride compound.
  • the acid binding agent in the present invention is an organic base or an inorganic base, and is preferably selected from the group consisting of pyridine, triethylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, potassium carbonate, sodium carbonate, Any of sodium hydrogencarbonate, potassium hydroxide, and sodium hydroxide.
  • the aprotic organic solvent is selected from any one of methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoramide.
  • the polymerization temperature is -5 to 15 ° C
  • the reaction time is 1 to 18 hours
  • the polymerization is carried out under the protection of an inert gas.
  • a specific film forming method is: dissolving the triptycene polymer in an aprotic organic solvent, vacuum degassing and standing to obtain a casting solution, and coating the casting solution on the support.
  • the oven is dried to obtain a tripentyl polymer separation membrane; under a preferred condition, the drying temperature is from 40 ° C to 150 ° C and the drying time is from 2 hours to 96 hours.
  • the aprotic organic solvent is selected from the group consisting of methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, dioxane, and hexamethylphosphoramide. Any of them.
  • the concentration of the casting solution is from 0.5 to 25% by weight, preferably from 1 to 20% by weight, further preferably from 5 to 15% by weight.
  • the support in the present invention is selected from an organic material base film or an inorganic material base film, and is preferably any one of polytetrafluoroethylene, cellulose acetate, and ceramic.
  • the three-dimensional network-like microporous polymer material is favored by researchers because of its special microporous structure, excellent mechanical properties and thermal stability, and is currently the most promising gas separation membrane material.
  • due to the presence of the network structure it is difficult to dissolve in common solvents, and its application in the separation membrane is limited.
  • the invention overcomes the defects that the VOCs separation membrane prepared by the reticulated polyamide material is insoluble in common solvent, has poor film forming property, easy aging and low separation efficiency.
  • the VOCs separation performance of the polyamide membrane can be effectively adjusted to achieve different separation requirements.
  • Figure 1 is a SEM electron micrograph of a cross section of the separation membrane obtained by the present invention.
  • Figure 3 is a SEM digital image of the surface of the separation membrane obtained by the present invention.
  • Figure 4 is a hydrogen spectrum diagram of the product prepared in Example 1 of the present invention.
  • Figure 5 is a hydrogen spectrum diagram of the product prepared in Example 5 of the present invention.
  • Figure 6 is a carbon spectrum of the product prepared in Example 5 of the present invention.
  • Figure 7 is a hydrogen spectrum diagram of the product prepared in Example 6 of the present invention.
  • the left picture shows a three-disc alkenyl polymer separation composite film; the right picture shows a polytetrafluoroethylene base film.
  • Pp is the VOCs concentration (ppm) on the permeate side
  • Pb is the VOCs concentration (ppm) on the raw material side
  • R is the rejection rate.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, hexamethylphosphoramide aprotic polar solvent at room temperature.
  • the separation performance of the composite membrane obtained in this example was tested for the N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.24 L/m 2 min.
  • the concentration of cyclohexane was measured. It was reduced from 30,000 ppm on the raw material side to 90 ppm on the permeate side, and the rejection was 99.7%.
  • the separation performance of the composite membrane obtained in this example was tested for N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.10 L/m 2 min.
  • the concentration of cyclohexane was measured. It was reduced from 30,000 ppm on the raw material side to 12 ppm on the permeate side, and the rejection was 99.96%.
  • Example 4 The target product prepared in Example 1 was subjected to nuclear magnetic resonance analysis, wherein the hydrogen spectrum is shown in Fig. 4.
  • the specific carbon spectrum and hydrogen spectrum analysis data are as follows:
  • ⁇ 8.12 ppm is the absorption peak of the benzene ring hydrogen atom in 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether
  • ⁇ 10.15 is a characteristic peak of a hydrogen atom of two amide groups.
  • ⁇ 115-136 ppm is the carbon absorption peak on the benzene ring of 2,6,14-triaminotripyceine and 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether
  • Example 1 The product obtained in Example 1 was 2.62 g, and the yield was calculated to be 90.34%.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, hexamethylphosphoramide aprotic polar solvent at room temperature.
  • the separation performance of the composite membrane obtained in this example was tested for N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.25 L/m 2 min.
  • the concentration of cyclohexane was measured. From 30000 ppm on the raw material side to 120 ppm on the permeate side, the rejection was 99.6%.
  • the target product prepared in Example 2 was subjected to nuclear magnetic resonance analysis, and the specific carbon spectrum and hydrogen spectrum analysis data were as follows:
  • ⁇ 2.0-2.1, 2.2-2.3ppm is the characteristic absorption peak of hydrogen atom of glutaryl chloride
  • ⁇ 10.2 is a characteristic absorption peak of hydrogen atoms of two amide groups.
  • ⁇ 46ppm and 54ppm are characteristic absorption peaks at the carbon of 2,7,14-triaminotriptyrene bridgehead
  • Example 2 The product obtained in Example 2 was 1.08 g, and the yield was calculated to be 84.77%.
  • the precipitate was filtered and washed with methanol for 3 to 4 times, the precipitate was dried under vacuum at 70 °C.
  • the prepared polymer is purified and dried, and then the composite film is prepared by dissolving in the aprotic solution, and the composite film has higher uniformity and better separation performance.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, hexamethylphosphoramide aprotic polar solvent at room temperature.
  • the separation performance of the composite membrane obtained in this example was tested for the N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.32 L/m 2 min.
  • the cyclohexane concentration was measured. From 30000 ppm on the raw material side to 240 ppm on the permeate side, the rejection was 99.2%.
  • the target product prepared in Example 3 was subjected to nuclear magnetic resonance analysis, and the specific carbon spectrum and hydrogen spectrum analysis data were as follows:
  • ⁇ 1.6-1.7ppm
  • 2.3-2.4ppm is the characteristic absorption peak of hydrogen atom on adipyl chloride
  • ⁇ 14.5 ppm is the characteristic absorption peak of two methyl carbons on the 9,10-dimethyl-2,6,14-triaminotriptyrene bridge carbon
  • ⁇ 25-26, 36-38ppm is the characteristic absorption peak of carbon atom on adipyl chloride
  • Example 3 The product obtained in Example 3 was 1.63 g, and the yield was 85.79%.
  • the precipitate was filtered and washed with methanol for 3 to 4 times, the precipitate was dried under vacuum at 70 °C.
  • the prepared polymer is purified and dried, and then the composite film is prepared by dissolving in the aprotic solution, and the composite film has higher uniformity and better separation performance.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrene at room temperature.
  • a pyrrolidone, hexamethylphosphoramide aprotic polar solvent were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in di
  • the separation performance of the composite membrane obtained in this example was tested for the N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.31 L/m 2 min.
  • the cyclohexane concentration was measured. From 30,000 ppm on the raw material side to 273 ppm on the permeate side, the rejection was 99.09%.
  • the target product prepared in Example 4 was subjected to nuclear magnetic resonance analysis, and the specific carbon spectrum and hydrogen spectrum analysis data were as follows:
  • ⁇ 13.5 ppm is the absorption peak of 9,10-dimethyl-2,6,14-triaminotriptyr 9, methyl carbon at the 10 position
  • Example 4 The product obtained in Example 4 was 1.27 g, and the yield was calculated to be 84.33%.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, hexamethylphosphoramide aprotic polar solvent at room temperature.
  • the separation performance of the composite membrane obtained in this example was tested for N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.36 L/m 2 min.
  • the concentration of cyclohexane was measured. From 30,000 ppm on the raw material side to 276 ppm on the permeate side, the rejection was 99.08%.
  • Example 5 The target product prepared in Example 5 was subjected to nuclear magnetic resonance analysis.
  • the specific hydrogen spectrum (Fig. 5) and carbon spectrum (Fig. 6) were analyzed as follows:
  • Example 5 The product obtained in Example 5 was 1.12 g, and the yield was calculated to be 88.47%.
  • the dried precipitate was tested for solubility.
  • the solvents were chloroform, water, methylpyrrolidone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, and diethyl ether. , cyclohexane, n-heptane.
  • the test results showed that the precipitate was soluble in dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, hexamethylphosphoramide aprotic polar solvent at room temperature.
  • the separation performance of the composite membrane obtained in this example was tested for the N 2 /C 6 H 6 system.
  • the permeation flow rate was 0.32 L/m 2 min.
  • the cyclohexane concentration was measured. It was reduced from 30,000 ppm on the raw material side to 150 ppm on the permeate side, and the rejection was 99.5%.
  • Example 6 The target product prepared in Example 6 was subjected to nuclear magnetic resonance analysis, and the specific hydrogen spectrum (Fig. 7) and carbon spectrum analysis data were as follows:
  • Example 6 The product obtained in Example 6 was 1.42 g, and the yield was 86.58%.
  • Example 3 Repeat the method of Example 3 in the patent CN201510883253.2, using 2,6,1 4-triaminotripycenes, sebacic acid chloride as the main monomer for synthesis, pyridine as the acid binding agent, and methylpyrrolidone as the solvent for the synthesis reaction.
  • the specific steps are as follows: 1 mol of 2,6,1 4-triaminotripyceine, 3 mol of pyridine, 2 mol of sebacic acid chloride is added to the solution of methylpyrrolidone and stirred to dissolve at a temperature of 2 ° C (nitrogen protection) Under the conditions, the reaction was carried out for 3.5 hours, and after the completion of the reaction, the temperature was raised to room temperature and then deionized water was added for precipitation. After the precipitate was filtered and washed with methanol, the precipitate was dried under vacuum at 80 °C.

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Abstract

L'invention concerne également un procédé de fabrication de film support polymère de triptycène. Le procédé consiste à effectuer, à l'aide d'un triptycène avec un groupe fonctionnel actif, un dichlorure d'oxalyle et une diamine comprenant une liaison éther en tant que monomères, une réaction de polymérisation dans un solvant organique non protoné en présence d'un agent liant l'acide; à verser une solution polymère de la réaction dans de l'eau déminéralisée pour précipitation, à filtrer un précipité puis à laver avec du méthanol, à sécher et à obtenir un polymère de triptycène; et à dissoudre le polymère de triptycène dans une solution organique non protonée pour former une solution de coulage, puis le revêtement d'un support avec la solution de coulage puis le séchage pour obtenir le film support de polymère de triptycène.
PCT/CN2017/081790 2016-07-07 2017-04-25 Procédé de fabrication d'un film polymère poreux WO2018006635A1 (fr)

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EP17803762.8A EP3323500B1 (fr) 2016-07-07 2017-04-25 Procédé de fabrication d'un film polymère poreux
US15/579,205 US10799836B2 (en) 2016-07-07 2017-04-25 Preparation method for triptyl polymer separation membrane

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CN106955605B (zh) * 2017-05-17 2019-10-11 南京工业大学 一种聚酰胺VOCs截留型聚合物分离膜及其制备方法
CN108619924B (zh) * 2018-05-03 2021-04-27 南京工业大学 一种三蝶烯基聚酰亚胺分离膜
CN109929117B (zh) * 2019-01-15 2021-04-30 浙江大学宁波理工学院 一种磷氮型刚性骨架多孔阻燃剂及其制备方法和应用
CN110756059B (zh) * 2019-11-04 2021-12-03 华东理工大学 一种以多孔离子聚合物为分散相的混合基质膜的制备方法及其气体分离的应用
CN111111475B (zh) * 2020-01-15 2022-03-22 南京工业大学 一种氧化石墨烯改性三蝶烯基聚酰胺分离膜的制备方法
CN111282459A (zh) * 2020-04-02 2020-06-16 贵州省材料产业技术研究院 铸膜液及其制备方法、对bpa具有选择性分离的膜及其制备方法与应用
CN111499859B (zh) * 2020-04-29 2023-03-10 镇江利德尔复合材料有限公司 一种低介电特性的含氟聚醚及其制备方法
CN111821861B (zh) * 2020-08-21 2022-01-07 烟台大学 一种星型分子化合物制备高通量有机溶剂纳滤膜的方法
CN112516810B (zh) * 2020-11-11 2022-08-16 南京工业大学 一种纳滤膜的制造方法及装置
CN112390943B (zh) * 2020-11-17 2022-03-04 北京理工大学 一种五蝶烯类功能材料、制备方法及其应用
CN112708341A (zh) * 2020-12-18 2021-04-27 合众（佛山）化工有限公司 一种三碟烯衍生物改性聚氨酯树脂水性涂料
CN112646114A (zh) * 2020-12-18 2021-04-13 合众（佛山）化工有限公司 三碟烯衍生物改性聚氨酯水性树脂及其制备方法
CN112957928B (zh) * 2021-02-23 2022-02-22 北京工商大学 一种微孔聚合物复合膜及其制备方法
CN113444242B (zh) * 2021-07-16 2022-05-31 黑龙江大学 以三蝶烯为中心含甲氧基三苯胺类聚酰胺及其制备方法和应用
CN115869788B (zh) * 2021-09-27 2023-07-14 中国石油化工股份有限公司 具有三蝶烯基结构的聚酰亚胺无规共聚物及其制备方法和应用
CN114163616B (zh) * 2021-12-21 2023-07-14 郑州大学 一种三聚氰胺功能化多孔有机聚合物及其制备方法和应用

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JP2018523562A (ja) 2018-08-23
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US10799836B2 (en) 2020-10-13
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